KR20180121796A - Improved deposits or layers for microporous membranes, improved membranes, improved lithium cell separators, improved cells, improved high-voltage lithium batteries, and related methods - Google Patents

Abstract

In at least selected embodiments, methods are provided that relate to new or improved deposits, layers, membranes, porous membranes, microporous membranes, battery separators, batteries, high voltage batteries, systems, methods, and / or their manufacture and / Or described. In at least certain embodiments, the improved membrane may comprise at least one polyphase metal or metal oxide deposition layer stable to 5 volts in the cell. In at least certain embodiments, the polyphase deposition layer provides improved charge / discharge capacity, improved wettability and / or adequate moisture retention, improved mechanical strength, conductive layer, improved adhesion, improved coating adhesion, and the like. By depositing a multiphasic metal or metal oxide matrix on the membrane, the modified membrane can have improved impedance / charge transfer, dielectric breakdown, and / or improved safety. By using the ultra-thin deposition layer, the energy density of the battery can be increased. The polyphase deposition material is preferably a super thin layer of metal or metal oxide applied to the porous membrane through a deposition technique using an external energy source such as laser, pulsed laser or microwave pulsed laser deposition. According to at least certain embodiments, the improved cell separator or cell separator membrane described herein may have at least a conductive deposit layer on the side facing the cathode, and in some embodiments may be embedded between and / or within the polyolefin membranes .

Description

Improved deposits or layers for microporous membranes, improved membranes, improved lithium cell separators, improved cells, improved high-voltage lithium batteries, and related methods

This application claims priority to and benefit of U.S. Provisional Patent Application No. 62 / 314,656, filed on March 29, 2016, the entire contents of which are hereby incorporated by reference.

At least in selected embodiments, the present invention provides a novel, improved or optimized deposition, layer, membrane, porous membrane, microporous membrane, composite membrane, battery separator, composite separator, separator with at least one conductive layer, / RTI > and / or their manufacture and / or use. At least in certain embodiments, the present invention relates to novel or improved porous membranes and methods of making such membranes. The improved membrane may comprise at least one multi-phase metal or metal oxide deposition layer stable to 5 volts or 7 volts in the cell. In at least certain embodiments, the polyphase deposition layer provides improved charge / discharge capacity. In at least certain selected embodiments, the polyphase deposition layer provides improved wettability and / or adequate moisture retention. In at least certain other embodiments, the polyphase deposition layer provides improved mechanical strength. By depositing a multiphasic metal or metal oxide matrix on the membrane, the modified membrane can have improved impedance / charge transfer, dielectric breakdown, and / or improved safety. By using an ultra-thin deposition layer, the energy density of the cell can be increased. The polyphase deposition material is preferably a super thin layer of metal or metal oxide applied to the porous membrane through a deposition technique using an external energy source such as laser, pulsed laser or microwave pulsed laser deposition. According to at least certain embodiments, the improved battery separator or battery separator membrane described herein may have a conductive deposit layer at least on the side facing the cathode, and in some embodiments may be embedded between and / or within the polyolefin membranes , One or more coatings or treatments. According to at least a selected embodiment, the present invention provides a novel or improved porous membrane or substrate, a separator membrane, a separator, a composite, an electrochemical device, a cell, a cell; Methods of making such membranes or substrates, separators, cells and / or cells; And / or methods of using such membranes or substrates, separators, cells, and / or cells.

The use of ceramic-containing polymer coatings is a known method of improving the performance of microporous membranes commonly used in lithium ion batteries. The coating can be applied to one or both sides of the separator. Conventional coating techniques include tip coatings, knives, gravure, curtains and sprays, and these coatings have been found to be thick and non-uniform. More recently, more advanced deposition techniques have been utilized to provide uniformity and to reduce coating thicknesses from 2 to 6 microns to several nanometers. It is believed that the metal and metal oxides provide benefits to the separator having crystalline phases that are critical for determining in-situ cell performance. For example, aluminum oxides have been introduced into many ceramic coatings due to their mechanical strength, chemical stability and electrochemical properties. Aluminum oxide (alumina) can be found in many crystalline or homogeneous polymorphs (alpha, gamma, eta, delta, kappa, xi, etc.). The alpha phase is thermodynamically stable and chemically inert and has been shown to be suitable for high temperature applications. The formation of aluminum oxide on the porous membrane can be achieved using chemical and physical vapor deposition of a variety of techniques. The steady-state transformation in which the aluminum oxide moves at temperatures higher than 500 ° C can only be achieved by using physical vapor deposition. As temperature increases, some homogeneous bodies of alumina may exist (γ → δ / θ → α). Due to the proper properties, pure alpha-phase aluminum oxide is preferred for ceramic coatings for porous films. However, to achieve electrochemical and oxidation protection properties in microporous films, and more specifically in battery separators, layers of pure a-phase aluminum oxide require a few microns in thickness and often exhibit inconsistent performance results.

With the continued development of battery performance and capacity, there is a need for improved separators, such as, for example, greater strength, thinner separators, functionalized separators, and the like. It may also be necessary to improve the final composition of the coating to balance between thickness and cell performance.

At least for a selected embodiment, aspect or purpose, the present invention or the present invention can address the need or issue and / or can be applied to new or improved deposits, layers, membranes, porous membranes, microporous membranes, composite membranes, , A composite separator, a separator having one or more conductive layers, a battery, and / or methods of manufacture and use thereof. At least in certain embodiments, the present invention relates to novel or improved porous membranes and methods of making such membranes. The improved membrane may include at least one polyphase metal or metal oxide deposition layer that is stable to 5 volts or 7 volts in the cell. In at least certain embodiments, the polyphase deposition layer provides improved charge / discharge capacity. In at least certain selected embodiments, the polyphase deposition layer provides improved wettability and / or adequate moisture retention. In at least certain other embodiments, the polyphase deposition layer provides improved mechanical strength. By depositing a multiphasic metal or metal oxide matrix on the membrane, the modified membrane can have improved impedance / charge transfer, dielectric breakdown, and / or improved safety. By using the ultra-thin deposition layer, the energy density of the battery can be increased. The polyphase deposition material is preferably a super thin layer of metal or metal oxide applied to the porous membrane through a deposition technique using an external energy source such as laser, pulsed laser or microwave pulsed laser deposition. According to at least certain embodiments, the improved battery separator or battery separator membrane described herein may have a conductive deposit layer at least on the side facing the cathode, and in some embodiments may be embedded between and / or within the polyolefin membranes , One or more coatings or treatments. According to at least a selected embodiment, the present invention provides a novel or improved porous membrane or substrate, a separator membrane, a separator, a composite, an electrochemical device, a cell, a cell; Methods of making such membranes or substrates, separators, cells and / or cells; And / or methods of using such membranes or substrates, separators, cells, and / or cells.

According to at least a selected embodiment, aspect or object, the present invention or the present invention may address the need or issue, and / or may include new or improved or optimized deposits, layers, membranes, porous membranes, microporous membranes, Membrane, cell separator, battery, cell, and / or methods of manufacture and use thereof. At least in certain embodiments, the present invention relates to novel or improved porous membranes and methods of making such membranes. The improved membrane may include at least one poly-phase metal or metal oxide deposit layer stable on the battery in at least one side, which is stable up to 7 volts. In at least certain embodiments, the polyphase deposition layer provides improved charge / discharge capacity. In at least certain selected embodiments, the polyphase deposition layer provides improved wettability and / or adequate moisture retention. In at least certain other embodiments, the polyphase deposition layer provides improved oxidation resistance and / or mechanical strength. By depositing a multiphasic metal or metal oxide matrix on the membrane, the modified membrane can have improved impedance / charge transfer, dielectric breakdown, and / or improved safety. By using the ultra-thin deposition layer, the energy density of the battery can be increased. The polyphase deposition material is preferably a super thin layer of metal or metal oxide applied to the porous membrane through a deposition technique using an external energy source such as laser, pulsed laser or microwave pulsed laser deposition. According to at least certain embodiments, the improved battery separator or battery separator membrane described herein may have a conductive or non-conductive deposit, such as a conductive layer, at least on the side facing the cathode, and in some embodiments, between the polyolefin membranes and / Or may be embedded in the interior. According to at least a selected embodiment, the present invention provides a novel or improved porous membrane or substrate, a separator membrane, a separator, a composite, an oxidation resistant deposition layer, an oxidation resistant membrane, an electrochemical device, a cell, a cell; Methods of making such membranes or substrates, separators, cells and / or cells; And / or methods of using such membranes or substrates, separators, cells, and / or cells.

According to at least a selected embodiment, aspect or object, the present invention or the present invention is able to address the need or issue and / or to provide a porous membrane with an ultra-thin polyphase metal or metal oxide deposition layer, improved charge / discharge capacity, Transfer, and stability of up to 7 volts in an electrochemical cell.

According to a particular embodiment, the separator membrane described herein is directed to a microporous separator membrane having an ultra-thin polyphase metal oxide deposition layer, wherein the deposition layer has a thickness of 5 m or less, preferably 1 m or less, more preferably 500 nm or less .

At least in certain embodiments, the separator membranes described herein include, but are not limited to, alpha-phase aluminum oxide and boehmite (or boehmite or aluminum oxide hydroxide (gamma -AlO (OH)) minerals, (a component of a metal oxide (bauxite)).

According to at least a selected embodiment, aspect or object, the present invention or the present invention can address the need or issue, and / or can provide an ultra-thin polyphase metal or metal oxide deposit layer to the porous membrane, A layer, a material, or a coating on or on top of at least a portion of the metal oxide deposition layer.

According to a particular embodiment, the separator membrane described herein is directed to a microporous separator membrane having at least one conductive, semi-conductive or non-conductive deposit layer on at least one side thereof, , Semi-conductive or non-conductive deposits, treatments, layers, materials or coatings.

At least in certain embodiments, the separator membranes described herein include, but are not limited to, alpha phase aluminum oxide and boehmite (or a component of boehmite or aluminum oxide hydroxide (gamma -AlO (OH)) mineral, aluminum light or bauxite) And at least one of a conductive, semi-conductive or non-conductive deposition material, a treatment material, a layer, a conductive layer, Materials or coatings.

The oxidation resistant deposit layer of the present invention in a microporous membrane or substrate for a lithium cell, such as a separator membrane or separator for a lithium secondary battery, a lithium ion battery or a lithium polymer battery, may be at least on the face of the separator membrane facing the cathode, Layer can be ultra-thin at the interface of the separator and the cathode and can be stable at voltages up to 7 volts in high voltage battery systems and / or can prevent trickle charging at high voltages up to 7 volts in a lithium battery It is possible to provide an ultra-thin high oxidation-resistant microporous separator, and / or to provide improved charging capacity and / or speed of movement.

In accordance with at least certain selected embodiments, the present invention provides an ultra thin polyimide deposition that provides oxidation protection, maintained or improved porosity, maintained or improved mechanical strength, maintained or improved shutdown behavior, and / or maintained or improved moisture content, Layers or coatings. Deposits, layers or coatings are preferably deposited onto a substrate by physical vapor deposition (PVD), chemical vapor deposition (CVD), pulsed laser deposition (PLD), atomic layer deposition (ALD), or microwave pulsed laser deposition (USPLD) ECAP), sputtering and / or E-beam, and more preferably by physical vapor deposition (PVD), pulsed laser deposition (PLD), microwave pulse laser deposition (USPLD)

Figure 1 includes a scanning electron micrograph (SEM) image of the surface of a coated or modified Celgard® 2500 microporous membrane (uncoated side) of Inventive Example 1 (EX 1) at 5,000 × magnification.
Figure 2 includes a scanning electron micrograph (SEM) image of the surface of the coated surface of the Example 1 Cell Guard 2500 microporous membrane of Figure 1 coated with 2 탆 Al ₂ O ₃ at 5,000 × magnification.
Figure 3 includes a scanning electron micrograph (SEM) image of the coated surface of the Example 1 Cell Guard 2500 microporous membrane of Figure 2 coated with 2 탆 Al ₂ O ₃ at 20,000 × magnification.
Figure 4 includes a scanning electron micrograph (SEM) image of a cross-section of Example 1 Cell Guard 2500 microporous membrane coated with 2 탆 Al ₂ O ₃ at 1,500 × magnification.
Figure 5 includes a scanning electron micrograph (SEM) image of a partial cross-section of the Example 1 Cell Guard 2500 microporous membrane of Figure 4 coated with 2 탆 Al ₂ O ₃ at 10,000 × magnification.
Figure 6 includes a scanning electron micrograph (SEM) image of the surface of the coated side of the Example 2 Cell Guard 2500 microporous membrane coated with 20 nm Al ₂ O ₃ at 5,000 × magnification.
Figure 7 includes a scanning electron micrograph (SEM) image of the coated surface of the coated Example 2 Cell Guard 2500 microporous membrane of Figure 6 coated with 20 nm Al ₂ O ₃ at 20,000 × magnification.
Figure 8 shows a comparison of Example 1 (Ex 1) coated with 2 탆 Al ₂ O ₃ , which shows the peak of alpha phase Al ₂ O ₃ and boehmite, compared to other PVD products as Comparative Example 2 (CE2) Or upper line).
Figure 9 shows a comparison of Example 1 (EX 1) coated with 2 탆 Al ₂ O ₃ (black or lower), which shows a peak of alpha phase Al ₂ O ₃ and boehmite compared to other PVD products (CE 1, CE 2) Line). ≪ / RTI >
10A and 10B are front and back surface images of an exemplary PVD treated membrane and a PVD treated membrane having a ceramic coating on the PVD treated surface, respectively.
FIG. 11 is a schematic end view or cross-sectional view of the exemplary ceramic coated PVD treated membrane or film of FIG. 10b.
12A and 12B are cross-sectional SEM images of the exemplary ceramic coated PVD treated membrane or film of Fig. 10B, respectively, at 2,700 x magnification and 20,000 x magnification.

At least for a selected embodiment, aspect or purpose, the present invention or the present invention can address the need or issue and / or can be applied to new or improved deposits, layers, membranes, porous membranes, microporous membranes, composite membranes, , A composite separator, a separator having one or more conductive layers, a battery, and / or methods of manufacture and use thereof. At least in certain embodiments, the present invention relates to novel or improved porous membranes and methods of making such membranes. The improved membrane may include at least one polyphase metal or metal oxide deposition layer that is stable to 5 volts or 7 volts in the cell. In at least certain embodiments, the polyphase deposition layer provides improved charge / discharge capacity. In at least certain selected embodiments, the polyphase deposition layer provides improved wettability and / or adequate moisture retention. In at least certain other embodiments, the polyphase deposition layer provides improved mechanical strength. By depositing a multiphasic metal or metal oxide matrix on the membrane, the modified membrane can have improved impedance / charge transfer, dielectric breakdown, and / or improved safety. By using the ultra-thin deposition layer, the energy density of the battery can be increased. The polyphase deposition material is preferably a super thin layer of metal or metal oxide applied to the porous membrane through a deposition technique using an external energy source such as laser, pulsed laser or microwave pulsed laser deposition. According to at least certain embodiments, the improved battery separator or battery separator membrane described herein may have a conductive deposit layer at least on the side facing the cathode, and in some embodiments may be embedded between and / or within the polyolefin membranes , One or more coatings or treatments. According to at least a selected embodiment, the present invention provides a novel or improved porous membrane or substrate, a separator membrane, a separator, a composite, an electrochemical device, a cell, a cell; Methods of making such membranes or substrates, separators, cells and / or cells; And / or methods of using such membranes or substrates, separators, cells, and / or cells.

In at least selected embodiments, the present invention or the present invention relates to new or improved porous membranes and methods of making such membranes. The improved membrane may preferably include at least one polyphase metal or metal oxide deposition layer that is stable up to 7 volts in the cell. In at least certain embodiments, the polyphase deposition layer provides improved charge / discharge capacity. In at least certain selected embodiments, the polyphase deposition layer provides improved wettability and adequate moisture retention (less moisture). In at least certain embodiments, the polyphase deposition layer provides improved mechanical strength. By depositing a multiphase metal or metal oxide matrix (preferably having many alpha phases, Al ₂ O ₃ and boehmite, or having a high amorphous content), the membrane has improved impedance / charge transfer, It is possible to have safety. See Figures 1-9. By using the ultra-thin deposition layer, the energy density of the battery can be increased. See Figures 1-5, 8 and 9. Preferably, the polyphase deposition material utilizes an external energy source, such as a laser, pulsed laser or microwave pulse laser deposition, and uses a laser target material such as Al ₂ O ₃ , boehmite or both to form a high alpha phase Al ₂ O ₃ content, high amorphous or alpha phase Al ₂ O ₃ content, high alpha phase Al ₂ O ₃ and boehmite content, high alpha phase Al ₂ O ₃ and boehmite, alpha phase Al ₂ O ₃ and boehmite A superfine layer of a metal or metal oxide applied to a porous membrane through a deposition technique to form a deposition comprising a polyphase metal or metal oxide having a high degree of crystallinity for all. See Figures 1-5, 8 and 9.

Test Methods

FTIR - The sample was scanned 16 times in the transmission mode over a wavenumber range of 4000 - 450 cm ^-1 . The coated surface was directed to the beam.

The sample was scanned over a range of 20 - 45 degrees 2-decades with a step size of XRD - 0.02 and a residence time of 3 seconds. Samples were prepared so that the coated side was facing the beam.

Also, according to at least certain embodiments, the deposition layer of the inventive battery separator membrane described herein is a conductive deposition layer and may be at least on the side facing the cathode, and in some embodiments may be embedded between and / or within the polyolefin membranes . According to at least a selected embodiment, the deposition layer of the inventive battery separator membrane described herein is a non-conductive deposition layer and may be at least on the side facing the cathode, and in some embodiments may be embedded between and / or within the polyolefin membranes And / or may be coated with a polymer coating or a ceramic coating. According to at least certain embodiments, the deposition layer of the battery separator membrane of the present invention described herein is a conductive or non-conductive deposition layer and can be on at least one or both sides of the membrane, and the present or the present invention provides such new or improved porosity Membranes or substrates, separator membranes, separators, composites, electrochemical devices, batteries; Methods of making such membranes or substrates, separators and / or cells; And / or methods of using such membranes or substrates, separators, and / or cells.

Also, according to at least certain embodiments, the deposition layer of the battery separator membrane of the present invention described herein is a conductive deposition layer and may be at least on the side facing the anode, and in some embodiments may be embedded between polyolefin membranes and / And / or may be coated with one or more non-conductive layers or coatings, such as being coated with a polymer coating or a ceramic coating (with or without a polymeric binder). This conductive layer can be part of a cell or cell safety system that detects dendrite, short, heat and / or other potential failure modes. According to at least a selected embodiment, the deposition layer of the battery separator membrane of the present invention described herein is a non-conductive deposition layer and may be at least on the side facing the anode, and in some embodiments may be embedded between and within the polyolefin membranes And / or may be coated with a polymer coating or a ceramic coating.

At least in selected embodiments, the present invention relates to novel or improved or optimized deposits, layers, membranes, porous membranes, microporous membranes, cell separators, batteries, and / or their manufacture and use. At least in certain embodiments, the present invention relates to novel or improved porous membranes and methods of making such membranes. The improved membrane may comprise at least one polyphase metal or metal oxide deposition layer that is stable to 7 volts in the cell. In at least certain embodiments, the polyphase deposition layer provides improved charge / discharge capacity. In at least certain selected embodiments, the polyphase deposition layer provides improved wettability and / or adequate moisture retention. In at least certain other embodiments, the polyphase deposition layer provides improved mechanical strength. By depositing a multiphasic metal or metal oxide matrix on the membrane, the modified membrane can have improved impedance / charge transfer, dielectric breakdown, and / or improved safety. By using the ultra-thin deposition layer, the energy density of the battery can be increased. The polyphase deposition material is preferably a super thin layer of metal or metal oxide applied to the porous membrane through a deposition technique using an external energy source such as laser, pulsed laser or microwave pulsed laser deposition. According to at least certain embodiments, the improved cell separator or battery separator membrane described herein may have a conductive or non-conductive deposit, such as a conductive deposit layer at least on the face towards the cathode, and in some embodiments, between the polyolefin membranes / RTI > and / or < / RTI > According to at least a selected embodiment, the present invention provides a novel or improved porous membrane or substrate, a separator membrane, a separator, a composite, an electrochemical device, a cell, a cell; Methods of making such membranes or substrates, separators, cells and / or cells; And / or methods of using such membranes or substrates, separators, cells, and / or cells.

The improved membrane comprises a polyphase metal or metal oxide deposition layer that is stable up to 7 volts in the cell. In at least certain embodiments, the polyphase deposition layer provides improved charge / discharge capacity. In at least certain embodiments, the polyphase deposition layer provides improved wettability and / or adequate moisture retention. In at least certain embodiments, the polyphase deposition layer provides improved mechanical strength. By depositing a multiphasic metal or metal oxide matrix, the membrane can have improved impedance / charge transfer, dielectric breakdown, and improved safety. By using the ultra-thin deposition layer, the energy density of the battery can be increased. The polyphase deposition material is preferably a super thin layer of metal or metal oxide applied to the porous membrane through a deposition technique using an external energy source such as laser, pulsed laser or microwave pulsed laser deposition. According to at least certain embodiments, the deposition layer of the battery separator membrane described herein is a conductive deposition layer and may be at least on the side facing the cathode, and in some embodiments may be embedded between and / or within the polyolefin membranes. According to at least a selected embodiment, the present invention provides a novel or improved porous membrane or substrate, a separator membrane, a separator, a composite, an electrochemical device, a cell; Methods of making such membranes or substrates, separators and / or cells; And / or methods of using such membranes or substrates, separators, and / or cells.

10A-12B, and in accordance with one exemplary embodiment, FIG. 10A illustrates an exemplary PVD-treated microporous polypropylene (PP) membrane (Celgard® 2500) having a conductive deposition or layer (Al) And Fig. 10b shows an exemplary PVD treated membrane having a ceramic coating (CS) on the PVD treatment (Al). In this embodiment, the ceramic coating (CS) is a non-conductive, non-conductive (non-plasma treated), non-conductive (non-plasma treated, Binder and alumina particle ceramic coating.

[Table 1]

[Table 2]

11 is a schematic end view of an exemplary ceramic coated PVD treated membrane or film of FIG. 10B, including a 25 um vertical or thickness dimensioned membrane, a 20 nm Al deposition, and a ceramic coating with 4 um alumina particles, or Sectional view.

12A and 12B are cross-sectional SEM images of the ceramic coated PVD treated membrane or film of FIG. 10B showing a membrane, an Al vapor deposition and a ceramic coating layer, respectively, at 2,700x magnification and 20,000x magnification.

Such a ceramic coated PVD treated membrane or film may desirably have a powder fall of less than 0.03 and / or a coating peel force of greater than 100.

Co-owned U.S. Laid-Open Patent Application No. 2017/0025658, published Jan. 26, 2017, which is incorporated herein by reference in its entirety for all purposes, is incorporated herein by reference for example in the context of a particular porous membrane or substrate, separator membrane, separator, Device, battery; Methods of making such membranes or substrates, separators and / or cells; And / or methods of using such membranes or substrates, separators, and / or cells.

In at least a selected embodiment of the present invention, the present invention relates to new or improved deposits, layers, membranes, porous membranes, microporous membranes, battery separators, batteries, high voltage batteries, systems, methods, and / Methods are provided or described. In at least certain embodiments, the improved membrane may comprise at least one polyphase metal or metal oxide deposition layer stable to 5 volts in the cell. In at least certain embodiments, the polyphase deposition layer provides improved charge / discharge capacity, improved wettability and / or adequate moisture retention, improved mechanical strength, conductive layer, improved adhesion, improved coating adhesion, and the like. By depositing a multiphasic metal or metal oxide matrix on the membrane, the modified membrane can have improved impedance / charge transfer, dielectric breakdown, and / or improved safety. By using the ultra-thin deposition layer, the energy density of the battery can be increased. The polyphase deposition material is preferably a super thin layer of metal or metal oxide applied to the porous membrane through a deposition technique using an external energy source such as laser, pulsed laser or microwave pulsed laser deposition. According to at least certain embodiments, the improved cell separator or cell separator membrane described herein may have at least a conductive deposit layer on the side facing the cathode, and in some embodiments may be embedded between and / or within the polyolefin membranes . According to at least a selected embodiment, the present invention provides a novel or improved porous membrane or substrate, a separator membrane, a separator, a composite, an electrochemical device, a cell, a cell; Methods of making such membranes or substrates, separators, cells and / or cells; And / or methods of using such membranes or substrates, separators, cells, and / or cells.

According to at least a selected embodiment, aspect or object, the present invention provides a new or improved porous membrane or substrate, a separator membrane, a separator, a composite, an electrochemical device, a cell, a system, A vehicle, a product or an apparatus comprising such a membrane or substrate, a separator membrane, a separator, a composite, an electrochemical device, a cell, a cell or a system; Methods of making such membranes or substrates, separators, cells, systems and / or cells; And / or methods of using such membranes or substrates, separators, cells, systems and / or cells.

The present invention may be embodied in other forms without departing from the spirit or essential attributes thereof, and accordingly, the appended claims should be considered as illustrative of the scope of the invention, rather than the foregoing specification. Additionally, the invention exemplarily disclosed herein may be suitably practiced without any elements not specifically disclosed herein.

Claims (48)

A microporous membrane or substrate comprising a layer of polycrystalline metal and / or metal oxide on at least one side of a polymeric porous membrane, said layer being applied by a deposition method or technique. The method according to claim 1,
The deposition method or technique is a vapor deposition method or a laser deposition method, which is a microporous membrane or substrate. The method according to claim 1,
The membrane is a component of an electrochemical device, a microporous membrane or substrate. The method according to claim 1,
The membrane is a component of a micro-porous membrane or substrate. The method according to claim 1,
Wherein the membrane is a component of a supercapacitor or a bilayer capacitor. The method according to claim 1,
Wherein the membrane is a battery separator. The method according to claim 1,
Wherein the membrane is a lithium cell separator. The method according to claim 1,
Wherein the membrane is a primary or secondary cell separator. The method according to claim 1,
Wherein the membrane is a lithium primary or secondary cell separator. The method according to claim 1,
Wherein the membrane is a lithium secondary battery separator stable for oxidation in a lithium ion cell having a cell voltage of up to 7.0 volts or 7.0 volts and wherein the cell voltage is a measure of the potential difference between the two electrodes in a lithium ion battery. The method according to claim 1,
Wherein the membrane is a lithium secondary cell separator that is stable to oxidation in a lithium ion cell having cell voltages of up to 5.2 volts or 5.2 volts or higher and the cell voltage is a microporous membrane or a microporous membrane that is a measure of the potential difference between two electrodes in a lithium ion cell, materials. The method according to claim 1,
The deposition method or technique is selected from the group consisting of physical vapor deposition, atomic layer deposition, chemical vapor deposition, sputtering, laser plasma, or a microporous membrane or substrate. The method according to claim 1,
Wherein the inert metal element further comprises an inert metal element in the layer, wherein the inert metal element comprises gold, platinum and mixtures thereof. The method according to claim 1,
Wherein the reactive metal element further comprises a reactive metal element in the layer, wherein the reactive metal element comprises aluminum, nickel, copper, and mixtures thereof. The method according to claim 1,
The metal oxide is aluminum oxide (Al ₂ O _3), boehmite AlO (OH), silicon oxide, titanium oxide, transition metal oxide and a micro porous membrane substrate or mixtures thereof. The method according to claim 1,
The polymeric porous membrane is a microporous membrane or substrate comprising polyolefin, polyvinylidene fluoride (PVdF), polyethylene terephthalate (PET), woven fibers and / or nonwoven fibers. The method according to claim 1,
The membrane or substrate may be a single layer formed using a dry process, a wet process, a particle elongation process, a biaxially oriented polypropylene (BOPP) process, a beta-nucleated biaxially oriented polypropylene (BN-BOPP) process, Or a microporous membrane or substrate that is a multilayer membrane or substrate. 8. The method of claim 7,
Said layer being on the side of the separator facing the cathode. 8. The method of claim 7,
Said layer being on either side of the separator. 8. The method of claim 7,
Said layer being on the side of the separator facing the anode. 8. The method of claim 7,
The layer being on the side of the separator facing the cathode and the ceramic coating being on the side of the separator facing the anode. 8. The method of claim 7,
Wherein the layer is on both sides of the separator and the ceramic coating is on top of the layer on the side of the separator facing the anode. 8. The method of claim 7,
Wherein the layer is on the face of the separator facing the anode and the ceramic coating is on top of the layer on the face of the separator facing the anode. 8. The method of claim 7,
Wherein the layer is on the face of the separator facing the cathode and the ceramic coating is on top of the layer on the face of the separator facing the cathode. 8. The method of claim 7,
Wherein the layer is on both sides of the separator and the ceramic coating is on top of the layer on the side of the separator facing the cathode. 8. The method of claim 7,
Wherein the layer is on the face of the separator facing the anode and the ceramic coating is on the polymer porous membrane or on the other side of the substrate. 8. The method of claim 7,
The layer is on the face of the separator facing the cathode and the first ceramic coating is on top of the polymeric porous membrane facing the cathode or on the face of the separator and the second ceramic coating is on the side of the polymeric porous membrane or separator A microporous membrane or substrate applied to the other side. 8. The method of claim 7,
Wherein the layer is on both sides of the separator and the ceramic coating is on top of both layers. 8. The method of claim 7,
Wherein the layer is on the face of the separator facing the anode, the first ceramic coating is on top of the layer, and the second ceramic coating is on the other side of the separator facing the cathode. 8. The method of claim 7,
Wherein the metal and / or metal oxide comprises a reactive metal element, wherein the reactive metal element comprises aluminum, nickel, copper, and mixtures thereof, the reactive metal element being a microporous membrane that is partially or completely converted to an inert material, or materials. 8. The method of claim 7,
A microporous membrane or substrate is a part of a lithium cell having an electrolyte comprising a solvent and a lithium salt. 32. The method of claim 31,
The lithium salt comprises lithium hexafluorophosphate (LiPF ₆ ). A primary or secondary cell comprising the microporous membrane or substrate according to claim 1. Methods of depositing at least one polycrystalline layer of metal and / or metal oxide on a membrane or substrate include: laser deposition, pulsed laser deposition, microwave pulse laser deposition, vacuum deposition, physical vapor deposition, atomic layer deposition, chemical vapor deposition, Using a deposition method selected from the group consisting of combinations; And depositing at least one polycrystalline layer of metal and / or metal oxide on the membrane or substrate. 35. The method of claim 34,
Wherein the at least one deposited layer has a total thickness of less than 3 microns. 35. The method of claim 34,
Wherein the at least one deposited layer has a thickness of less than 2 占 퐉 in the microporous membrane. 35. The method of claim 34,
Wherein the at least one deposited layer has a thickness of less than 1 [mu] m. 35. The method of claim 34,
Wherein the at least one deposited layer has a thickness of less than 0.1 [mu] m. 35. The method of claim 34,
Wherein the at least one deposited layer has a thickness of less than 0.05 占 퐉. The method according to claim 1,
Wherein the membrane is a lithium secondary battery separator that is stable to oxidation in a lithium ion cell having a positive electrode potential of up to 7.2 volts or more relative to a Li / Li ⁺ reference electrode. The method according to claim 1,
Wherein said membrane is a lithium secondary battery separator stable to oxidation in a lithium ion cell having a positive electrode potential of up to 5.4 volts or more relative to a Li / Li ⁺ reference electrode. A conductive microporous membrane or substrate comprising a polymeric porous membrane having a conductive inorganic layer on the membrane, wherein the conductive inorganic layer comprises a polycrystalline layer of metal and / or metal oxide. 43. The method of claim 42,
Wherein the layer of conductive inorganic material is on at least one side of the polymeric porous membrane. 43. The method of claim 42,
Wherein the layer of conductive inorganic material is on at least one side of the polymeric porous membrane and the layer is a vacuum and / or vapor deposition layer. 43. The method of claim 42,
The polymeric porous membrane is a conductive microporous membrane or substrate comprising polyolefin, polyvinylidene fluoride (PVdF), polyethylene terephthalate (PET), woven fabric, nonwoven fabric or a mixture thereof. A cell comprising an ultra-thin polycrystalline metal or metal oxide deposition layer on a porous membrane, wherein the cell comprises one or more deposits, treatments, layers, materials or coatings on or on at least a portion of the ultra-thin polycrystalline metal or metal oxide deposit layer Separator. Conductive, or non-conductive deposition layer on at least a portion of at least a portion of the deposition layer, wherein at least one of a conductive, semi-conductive or non-conductive deposition material, A battery separator membrane comprising a coating. at least one surface of a deposition layer comprising a polyphase of a metal oxide comprising an alpha-phase aluminum oxide and / or a boehmite, wherein at least one conductive, semi-conductive or non- A battery separator membrane comprising a conductive deposit, a treated material, a layer, a material or a coating.

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